A copper-free Sandmeyer-type fluorosulfonylation reaction is reported. Utilizing Na2S2O5 and Selectfluor as the sulfur dioxide and fluorine sources, respectively, aryldiazonium salts were transformed into sulfonyl fluorides. The one-pot direct synthesis of sulfonyl fluorides from aromatic amines was also realized via in situ diazotization. The practicality of this method was demonstrated by the broad functional group tolerance, gram-scale synthesis, and late-stage fluorosulfonylation of natural products and pharmaceuticals.Ion-π interactions between the face of a molecular π-system and a cation or anion are among the strongest non-covalent interactions known, with applications throughout biochemistry and structural biology, molecular recognition and host-guest chemistry, as well as enzyme kinetics and organocatalysis. In this work, we examine the competing notions of selectivity and flexibility in this class of non-covalent interactions by investigating how certain π-systems can be promiscuous ion-π binders with the versatility to form favorable cation- and anion-π complexes. We focus our efforts on a detailed theoretical case study of the DNA/RNA nucleobases by first demonstrating that these π-systems are promiscuous ion-π binders with the biologically relevant Li+/Na+ cations and F-/Cl- anions via benchmark-quality quantum-mechanical binding energy curves computed at the CCSD(T)/CBS level of theory. Using a SAPT-based energy decomposition analysis, we explore the different physicochemical driving forces underlying the formatihould be common in nature.We report a simple and efficient visible-light-induced transition-metal-free hydrogenation of aryl halides. The combined visible light and base system is used to initiate the desired radical-mediated hydrogenation. A variety of aryl fluorides, chlorides, bromides, and iodides could be reduced to the corresponding (hetero)arenes with excellent yields under mild conditions. Various functional groups and other heterocyclic compounds are tolerated.A copper-catalyzed approach was disclosed for C(sp3)-C(sp2) bond formation via an α-arylation of carbonyl, and the subsequent oxidative dehydrogenation coupling occurred to form a C(sp3)-N bond, wherein O2 served as a green oxidant. This protocol provided a domino method for the synthesis of spiro[cyclohexane-1,12'-isoindolo[1,2-b]quinazolin]-10'-ones containing a nitrogen-substituted quaternary carbon center.Spin-orbit torque (SOT) switching of magnetization is a promising emerging technology for nonvolatile spintronic memory and logic applications. However, deterministic switching of perpendicular magnetization with SOTs requires an additional symmetry breaking, which is typically provided by an external magnetic field, making it impractical for applications. In this work, we disclose that by the insertion of a slightly asymmetric light-metal layer at the heavy metal-ferromagnet interface of SOT heterostructures, current-induced out-of-plane effective magnetic fields are introduced that enable deterministic switching without an external magnetic field. We obtain uniform perpendicular magnetic anisotropy and switching current density despite the asymmetry of the light-metal layer, and we show the scalability of our approach by studying device sizes that differ by 2 orders of magnitude. Our work provides a practical route for utilization of SOTs for magnetization switching on the wafer scale and paves the way for the practical application of SOT-based technology.A mild and efficient method for the vanadium-catalyzed intramolecular coupling of tethered free phenols is described. The corresponding phenol-dienone products are prepared directly in good yields with low catalyst loadings. Electronically diverse tethered phenol precursors are well tolerated, and the catalytic method was effectively applied as the key step in syntheses of three natural products and a synthetically useful morphinan alkaloid precursor.To understand the ligand-controlled palladium-catalyzed coupling of o-bromobenzaldehyde, N-tosylhydrazone, and methanol to give methyl 2-benzylbenzoic ester or methyl ether, we herein investigated the mechanisms which account for how C-C and C-O bonds are formed and why bidentate dppf/dppb ligands afford ester, whereas P(o-tolyl)3 ligand gives ether. https://www.selleckchem.com/products/ar-c155858.html The ester chemoselectivity of the bidentate ligands is attributed to the strong electron-donating effect that disfavors the C,Br-reductive elimination of the coupling intermediate of o-bromobenzaldehyde and N-tosylhydrazone.An efficient method for the one-pot synthesis of tetramic acid derivatives was developed utilizing tandem umpolung N-alkylation/reduction/cyclization of γ-hydrazono β-ketoester. By using this reaction as a key step, the total synthesis of the 3-spiro 7-hydroxamic acid tetralin which possesses an HDAC inhibitory activity was also achieved.An iron-catalyzed radical alkylazidation of electron-deficient alkenes is reported. Alkyl diacyl peroxides work as the alkyl source, and trimethylsilyl azide acts as the azido reservoir. This method features mild reaction conditions, wide substrate scope, and good functional group tolerance, providing a range of α-azido esters, an α-azido ketone, and an α-azido cyanide in high yields. These azides can be easily transferred into many kinds of amino acid derivatives.The chemistries selectively modifying recombinant proteins are valuable for the discovery and development of biologic therapeutics. We report here a Lys modification strategy that engages a Cys residue to covalently tether the reagents to the target that facilitates a proximity-driven intramolecular O-to-N acyl-transfer process yielding desired Lys-acylated products. We utilized GLP-1 as a case study, followed by desulfurization of the Cys mutation to native Ala regenerating the native sequence in a traceless fashion.Guided-wave plasmonic circuits are promising platforms for sensing, interconnection, and quantum applications in the subdiffraction regime. Nonetheless, the loss-confinement trade-off remains a collective bottleneck for plasmonic-enhanced optical processes. Here, we report a unique plasmonic waveguide architecture that can alleviate such trade-off and improve the efficiencies of plasmonic-based emission, light-matter-interaction, and detection simultaneously. Specifically, record experimental attributes such as normalized Purcell factor approaching 104, 10 dB amplitude modulation with less then 1 dB insertion loss and fJ-level switching energy, and photodetection sensitivity and internal quantum efficiency of -54 dBm and 6.4% respectively have been realized within our amorphous-based, coupled-mode plasmonic structure. The ability to support multiple optoelectronic phenomena while providing performance gains over existing plasmonic and dielectric counterparts offers a clear path toward reconfigurable, monolithic plasmonic circuits.